US4915809A - Carbon electrodes including trasition metal dispersed therein - Google Patents

Carbon electrodes including trasition metal dispersed therein Download PDF

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Publication number
US4915809A
US4915809A US07/267,616 US26761688A US4915809A US 4915809 A US4915809 A US 4915809A US 26761688 A US26761688 A US 26761688A US 4915809 A US4915809 A US 4915809A
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US
United States
Prior art keywords
transition metal
electrolytic cell
vanadium
cobalt
dispersed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07/267,616
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English (en)
Inventor
Oliver R. Brown
Martyn J. Wilmott
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sellafield Ltd
Original Assignee
British Nuclear Fuels PLC
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Filing date
Publication date
Application filed by British Nuclear Fuels PLC filed Critical British Nuclear Fuels PLC
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Publication of US4915809A publication Critical patent/US4915809A/en
Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/245—Fluorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/042—Electrodes formed of a single material
    • C25B11/043—Carbon, e.g. diamond or graphene

Definitions

  • This invention relates to carbon electrodes such as are used in the production of fluorine by electrolysis of a mixed molten salt electrolyte using a porous carbon anode, the electrolyte usually comprising potassium, fluoride and hydrogen fluoride.
  • a carbon electrode at least part of which has one or more transition metals atomically dispersed therein.
  • the transition metal(s) may be dispersed through the entire carbon electrode although it is within the ambit of the invention for transition metal doping to be confined to those parts of the electrode which, in use, are or will become (as a result of electrode material loss in the course of electrolysis) exposed to the electrolyte.
  • a carbon electrode comprising a consolidated mass of carbon particles and the residue of a carbonaceous binder, the particles and/or binder residue of at least part of the electrode having one or more transition metals substantially atomically dispersed therein.
  • a carbon electrode comprising a consolidated mass of carbon particles and the residue of a carbonaceous binder, the particles of at least part of the electrode having one or more transition metals dispersed therein.
  • the transition metal(s) may be dispersed within the particles by incorporating the transition metal within a precursor material which is subsequently carbonized and finely divided to produce the carbon particles and, in this event, it is preferred to combine the transition metal with the precursor while the latter is in a liquid phase so that atomic dispersion of the transition metal is facilitated.
  • the transition metal may be provided in the form of a thermally decomposable organic complex of the metal, eg. the transition metal combined with an organic ligand such as acetyl acetonate, and may be dissolved in a suitable liquid vehicle, such as furfuryl alcohol, for mixing with the liquid phase precursor.
  • the precursor may then be carbonized, the organic ligand being one which will decompose at temperatures within the range normally used in the carbonization of precursor materials for carbon electrode production.
  • the precursor may be pulverised to produce particles of conventional size for carbon electrode production, and the particles can then be combined with a suitable binder, such as pitch tar, consolidated and heat treated to produce a porous carbon electrode comprising the particles and the residue of the pitch tar.
  • the precursor may be a derivative of petroleum or coal-tar, eg. it may be a petroleum derivative from which petroleum coke is conventionally produced for use in carbon electrode manufacture.
  • the transition metal elements are preferably selected from nickel, vanadium and cobalt and may be used in combination, eg. both nickel and vanadium doping of the precursor and/or binder may be employed.
  • a coarser dispersion is within the scope of the invention and preferably the dispersion is such that an arbitrary slice of the electrode or electrode part having a thickness of the order of 10 -9 meters is sufficiently thick to wholly encompass at least one transition metal site.
  • the major part of the transition metal dopant is present as centers with diameters no greater than 1 ⁇ 10 -9 meters.
  • the or each transition metal is typically present in an amount less than 1.0 atom % and preferably up to about 0.1 atom %.
  • the invention has particular application to carbon anodes as used in fluorine-producing electrolytic cells. It is known that operation of fluorine cells leads to the formation at the anode surface of an extremely thin film of carbon monofluoride (CF) x --typically of the order of 10 -9 meters thick--which significantly increases the anode operating voltage needed for efficient cell operation.
  • CF carbon monofluoride
  • the introduction of a very fine dispersion of these transition metals ensures that transition metal ion sites (resulting from oxidation of the transition metal centers present in the fluoride film) are available within the thickness of the (CF) x film thereby facilitating electron transfer between the electrolyte and the anode.
  • the anode tends to erode and consequently the (CF) x film is continually following erosion of the anode surface and therefore encompasses fresh transition metal ion sites.
  • the possibility of enhancement of electron transfer by the transition metal ion sites is thought to counteract the effect of the (CF) x film formation which is believed to reduce the probability of electron transfer from HF 2 - species.
  • the presence of the transition metal dopants, nickel, cobalt and/or vanadium serves to reduce the anode overvoltage.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
US07/267,616 1986-08-01 1988-11-02 Carbon electrodes including trasition metal dispersed therein Expired - Fee Related US4915809A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8618909 1986-08-01
GB8618909A GB2193225B (en) 1986-08-01 1986-08-01 Carbon electrodes

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US07066145 Continuation 1987-06-25

Publications (1)

Publication Number Publication Date
US4915809A true US4915809A (en) 1990-04-10

Family

ID=10602130

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/267,616 Expired - Fee Related US4915809A (en) 1986-08-01 1988-11-02 Carbon electrodes including trasition metal dispersed therein

Country Status (8)

Country Link
US (1) US4915809A (fr)
EP (1) EP0255225B1 (fr)
JP (1) JPS6338593A (fr)
AU (1) AU597690B2 (fr)
CA (1) CA1315240C (fr)
DE (1) DE3766564D1 (fr)
GB (1) GB2193225B (fr)
ZA (1) ZA875309B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290413A (en) * 1991-07-26 1994-03-01 Minnesota Mining And Manufacturing Company Anodic electrode for electrochemical fluorine cell
US5580658A (en) * 1993-07-14 1996-12-03 Doryokuro Kakunenryo Kaihatsu Jigyodan Copper-carbon composite material with graded function and method for manufacturing the same
US6146506A (en) * 1993-09-03 2000-11-14 3M Innovative Properties Company Fluorine cell
CN109267098A (zh) * 2018-09-27 2019-01-25 四川大学 制氟阳极及其制备方法

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2729254B2 (ja) * 1988-08-05 1998-03-18 信淳 渡辺 低分極性炭素電極
JPH0784669B2 (ja) * 1988-11-11 1995-09-13 三井造船株式会社 炭素質電極
JPH03232988A (ja) * 1990-02-06 1991-10-16 Toyo Tanso Kk 炭素電極ならびにそれを用いるｈｆ含有溶融塩の電解方法及び装置
RU2118995C1 (ru) * 1996-07-01 1998-09-20 Ангарский электролизный химический комбинат Анод фторного среднетемпературного электролизера
EP3690081A4 (fr) 2017-09-27 2021-06-09 Sekisui Chemical Co., Ltd. Dispositif de réduction de dioxyde de carbone, et électrode poreuse
CN121039325A (zh) * 2023-12-27 2025-11-28 株式会社力森诺科 电解液制造装置、电解液制造方法以及氟气制造方法

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534638A (en) * 1947-12-17 1950-12-19 Harshaw Chem Corp Electrolytic production of fluorine
GB957168A (en) * 1959-10-02 1964-05-06 Ici Ltd Improvements in or relating to a process for the electrolytic production of fluorineand apparatus therefor
GB1078936A (en) * 1963-11-05 1967-08-09 Japan Atomic Energy Res Inst A process for preparing nuclear fuel elements of dispersed-in-graphite type
GB1137743A (en) * 1965-03-26 1968-12-27 Clevite Corp Fuel cell electrode
GB1277620A (en) * 1969-01-31 1972-06-14 Conradty Fa C Electrodes for electric arc furnaces
US4011374A (en) * 1975-12-02 1977-03-08 The United States Of America As Represented By The United States Energy Research And Development Administration Porous carbonaceous electrode structure and method for secondary electrochemical cell
US4086404A (en) * 1976-01-27 1978-04-25 The United States Of America As Represented By The United States Department Of Energy Electrode including porous particles with embedded active material for use in a secondary electrochemical cell
GB2054650A (en) * 1979-08-02 1981-02-18 Watanabe N Darbon anode used in electrolytic method of producing fluorine from a potassium fluoride and hydrogen fluoride mixed salt system
US4282074A (en) * 1980-07-07 1981-08-04 Ppg Industries, Inc. Electrolytic process utilizing a transition metal-graphite intercalation compound cathode
EP0163597A1 (fr) * 1984-04-27 1985-12-04 Schweizerische Aluminium Ag Procédé pour la diminution de la tendance d'oxydation aux températures élévées de la poudre de charbon ou articles de charbon fabriqués en utilisant ces poudres de charbon
US4568442A (en) * 1985-02-01 1986-02-04 The Dow Chemical Company Gas diffusion composite electrode having polymeric binder coated carbon layer
DE3538294A1 (de) * 1985-10-29 1987-04-30 Alusuisse Verfahren zur herabsetzung der bei temperaturen ueber 800(grad) c bestehenden oxidationsneigung von aus kohlepulver hergestellten anoden fuer die erzeugung von aluminium durch schmelzflusselektrolyse

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2334638A (en) * 1940-10-05 1943-11-16 Fort Orange Paper Company Bottle carrier
FR1474297A (fr) * 1965-03-26 1967-03-24 Clevite Corp électrode pour piles à combustible
JPS57200585A (en) * 1981-06-02 1982-12-08 Nikkei Giken:Kk Carbonaceous electrode plate for manufacture of fluorine by electrolysis
JPS5928581A (ja) * 1982-08-05 1984-02-15 Asahi Glass Co Ltd ガス拡散電極用材料
JPS60221591A (ja) * 1984-04-17 1985-11-06 Central Glass Co Ltd フツ素の製造方法

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534638A (en) * 1947-12-17 1950-12-19 Harshaw Chem Corp Electrolytic production of fluorine
GB957168A (en) * 1959-10-02 1964-05-06 Ici Ltd Improvements in or relating to a process for the electrolytic production of fluorineand apparatus therefor
GB1078936A (en) * 1963-11-05 1967-08-09 Japan Atomic Energy Res Inst A process for preparing nuclear fuel elements of dispersed-in-graphite type
GB1137743A (en) * 1965-03-26 1968-12-27 Clevite Corp Fuel cell electrode
GB1277620A (en) * 1969-01-31 1972-06-14 Conradty Fa C Electrodes for electric arc furnaces
US4011374A (en) * 1975-12-02 1977-03-08 The United States Of America As Represented By The United States Energy Research And Development Administration Porous carbonaceous electrode structure and method for secondary electrochemical cell
US4086404A (en) * 1976-01-27 1978-04-25 The United States Of America As Represented By The United States Department Of Energy Electrode including porous particles with embedded active material for use in a secondary electrochemical cell
GB2054650A (en) * 1979-08-02 1981-02-18 Watanabe N Darbon anode used in electrolytic method of producing fluorine from a potassium fluoride and hydrogen fluoride mixed salt system
US4312718A (en) * 1979-08-02 1982-01-26 Nobuatsu Watanabe Method for producing fluorine
US4282074A (en) * 1980-07-07 1981-08-04 Ppg Industries, Inc. Electrolytic process utilizing a transition metal-graphite intercalation compound cathode
EP0163597A1 (fr) * 1984-04-27 1985-12-04 Schweizerische Aluminium Ag Procédé pour la diminution de la tendance d'oxydation aux températures élévées de la poudre de charbon ou articles de charbon fabriqués en utilisant ces poudres de charbon
US4568442A (en) * 1985-02-01 1986-02-04 The Dow Chemical Company Gas diffusion composite electrode having polymeric binder coated carbon layer
DE3538294A1 (de) * 1985-10-29 1987-04-30 Alusuisse Verfahren zur herabsetzung der bei temperaturen ueber 800(grad) c bestehenden oxidationsneigung von aus kohlepulver hergestellten anoden fuer die erzeugung von aluminium durch schmelzflusselektrolyse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A. T. Kuhn (Editor), Industrial Electrochemical Processes, Elsevier Publishing Co., 1971. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5290413A (en) * 1991-07-26 1994-03-01 Minnesota Mining And Manufacturing Company Anodic electrode for electrochemical fluorine cell
US6063255A (en) * 1991-07-26 2000-05-16 3M Innovative Properties Company Anodic electrode for electrochemical fluorine cell
US5580658A (en) * 1993-07-14 1996-12-03 Doryokuro Kakunenryo Kaihatsu Jigyodan Copper-carbon composite material with graded function and method for manufacturing the same
US6146506A (en) * 1993-09-03 2000-11-14 3M Innovative Properties Company Fluorine cell
CN109267098A (zh) * 2018-09-27 2019-01-25 四川大学 制氟阳极及其制备方法

Also Published As

Publication number Publication date
JPS6338593A (ja) 1988-02-19
CA1315240C (fr) 1993-03-30
EP0255225A3 (en) 1988-12-21
ZA875309B (en) 1988-01-26
DE3766564D1 (de) 1991-01-17
EP0255225A2 (fr) 1988-02-03
GB2193225B (en) 1990-09-19
AU597690B2 (en) 1990-06-07
GB2193225A (en) 1988-02-03
AU7567187A (en) 1988-02-18
EP0255225B1 (fr) 1990-12-05
GB8618909D0 (en) 1986-09-10

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Effective date: 20020410